δ-Ferrocenyl-Komplexe des Rutheniums

Article abstract of DOI:10.1016/0022-328X(92)85065-5

The reactions of lithioferrocene (fcLi) and 1,1'-dilithioferrocene (FcLi2) with the halfsandwich ruthenium complexes CpRu(CO)2Cl, Cp^*Ru(CO)2Cl and (C6Me6)Ru(CO)Cl2 have been used to prepare the ferrocenyl compounds CpRu(CO)2Fc (1), Cp^*Ru(CO)2Fc (2) and (C6Me6)Ru(CO)(Cl)Fc (3), as well as the ferrocenylene compounds 2fc (4) and *Ru(CO)2>2fc (5), respectively. Photodecarbonylation of 1 and 2 in the presence of two-electron ligands (L = CN^tBu (a), PPh3 (b), PMe3 (c)) leads to chiral complexes of the type Cp^(*)Ru(CO)(L)Fc (1a-c, 2a-c); in the case of L = CN^tBu, further CO-substitution takes place to give Cp^(*)Ru(CN^tBu)2Fc (1d, 2d).Photo-induced reaction of 3 with excess trimethylphosphane, PMe3 (c), produces the octahedral complex mer-<(PMe3)3Ru(CO)(Cl)Fc> (6), whereas organolithiums (ⁿBuLi and p-TolLi, but not FcLi) react with 3 to give (C6Me6)Ru(CO)(R)Fc (R = ⁿBu (7a), p-Tol (7b)).Oxidation of 1, 2 and 3 by AgBF4 leads to paramagnetic salts such as (*)Ru(CO)2Fc>BF4 (1e, 2e) and <(C6Me6)Ru(CO)(Cl)Fc>BF4 (3e).All new complexes were characterized by IR, 1H and 13C NMR, and mass spectroscopy; the Cp and Cp^* compounds were also studied by cyclovoltammetry.